There is a demand for extremely sensitive and non-destructive analytical techniques, for use in a wide variety of fields including biological and chemical assays. Mass spectrometry is one widely-used analytical method, which relies on ionization of a target molecule. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI), which relies on a traditional preparation method, is limited by the necessity of co-crystallization of the analyte in a matrix. In addition, MALDI sensitivity, especially for low molecular weight analytes, is often limited by background noise due to ionization of matrix molecules. More recently-developed methods including DIOS have shown some success, but are limited in analyte scope. Nanostructure initiator mass spectrometry (NIMS) is a highly sensitive detection method, which has low background of direct analyzing a wide range of samples, such as biofluids, tissues and single cells. NIMS analysis uses a liquid initiator coated nanostructure surface that absorbs and transfers laser energy to analyte ions during the initiator vaporization phase. There is a need for designing mass spectrometry surfaces (e.g., NIMS surfaces) for increased metabolite detection sensitivity and coverage, and selective metabolite analysis.